Vat dyestuffs of the anthraquinone series



' dyestuils ofV the anthraquinone series.

Patented Aug. 26, Y193() UNITED STATES PATENT OFFICE KARL KRAUER AND GIIS'TAV nnss, 0E BASEL, SWITZERLAND, ASsIeNo'Es T'o THE FIRM SOCIETY or CHEMICAL IN'InIsTEY IN BAsLE, or BASEL, SWITZERLAND VAT V`nYEsTuEFs 0E THE ANTHBAQUINONE SERIES NoDrawng'. Application Ied October 10',- 1927, Serial No. 225,389, and in Switzerland October 20, 1926.

The present invention. refers to new vat It comprises the new vat dyestuis, their method of manufacture, and the material, which has been dyed with the new'products.

The vnew dyestuffs are obtained as follows f Ina rst Step the so-called diketoperylene dyestuffsof the general formula o Il benzoylv radical wherein'the one of the two ais stands for a which is linked in ahaposaion to as oo- Y group to the carbon atom Which is linked to the other'w, such as violanthrone or isoviolanthrone or the Substitution products of these dyestuifs, are converted, by treatment with sulphonating agents, such as sulphuric acidf monohydrate, chlorosulphonic acid or fum- Y ing sulphuric acid, into new sulphonic acids.

These new sulphonic acids,- the constitutionv `of which has notas yet been; ascertained,

dissolvejin water to violetto blue `solutions and with hydrosulphite and alkali yield bluish and green tints. Y "In a Second step thenew ysulphonic acids violetto blue vats which dye cotton Vviolet to are treated with hot alkalies; They are thus` changed into other new compounds',` appar- Vently hydroxy-compounds, which are dark powders yielding red-violet to blue alkaline vats which dye cotton blueto grey and olive tints, for the most and acids. n

In a third step these hydroxy-compounds are treated with etherying agents, such as alkylor aralkylhalides, acid esters, alde- 'hydes, acetals, and the like. There are thus obtained new dyestuffs, which form dark powderswhich dissolve in concentrated sul- Vphuric acid to blue solutions, yielding redviolet to blue vats which dye cotton grey to blue-green tints Vwhich have remarkable properties of fastness. Particularly valuable are the fastnessto chlorine and to light of their bright tints on cotton. These dyestuiis may be converted by chlorination` into halocrenated Idyestulls ofthe same properties. ike productsrnay be obtained by halogenatingthe products of the second step before the' treatment withfetherifying agents.

part sensitive to chlorine Example 1 l0 parts of violanthrone of thefformula O f K are dissolved in 100 kparts of sulphuric acid Inonohydrate. To this solution are added 30 parts of fuming sulphuri-acid of 24.- per cent Y strengthand the whole is heated for some hours at 125-1300'0. f After cooling,the mass poured into ice-water, and the blue occulent precipitate ispltere/d by suction andthen dissolved in hot Water. The solutionis filtered, and after it has been made feeblyA alkaline the Sodium Salt of the-new violanthrone acid is salted out with common salt,

sulphonic dilute common salt y and dimethyl violanthrone.

Like products are also obtained when sulphnric acid n'ionohydrate or chlorosulphonic aci is substituted for the uming sulphuric aci The colour tint of the dyestud may be shifted by addition of some other material to the mixture undergoing sulphonation. For instance, in sulphonating violanthrone as described in the iirst paragraph of this example, the addition of boric acid determines the production oa redder dyeing dyestuli.

Example 2 10 parts of violanthrone are dissolvedin 100 parts of fuming sulphuric acid of 24: per cent` strength. This solution is heated to 130 C. and stirred for 2 hours at 130 to 135 C. Aftercooling the sulphonation liquid is poured into ice water, dissolving the precipitate and salting out the sodium salt of the sulphoni'cacid thus producedwith common salt. The red-violet precipitate is then filtered and washed tree of acid with a solution of common salt.

The product dissolves in sulphuric acid to a violet blue solution and in water and dilute caustic soda solution to a red-violet solution. lf this alkaline solution is boiled for a long time a shift of color of the solution occurs toward green., From a blue vat cotton is dyed greenish-blue. The compound treated with hot alkali dyes from a blue vat green tints which are sensitive to acids.

acid theproduct treated with caustic soda solution dissolves to a red-violet solution.

Example 3 rInto 100V parts of fused caustic potash are introduced at 180O C. lOfparts ofthe violanthrone sulphonic acid of Example l; The

brown black melt is heated to 2709. and

Vstirredat this temperature for l hour; it is then dissolved in water, the solution boiled for some time and the precipitate thus pro- In sulphuric duced is liltered by suction and washed. The dyestuff thus obtained is a grey-black powder which dissolves in concentrated sulphuric acid to a blue solution and yields a red-violet vat which dyes cotton blue-grey tints, which .f

Example J;

120 parts of caustic potash areintroduced Y into parts of alcohol. After heating' to 'i 'i60o C. 20 parts oic the green sodium salt obtained as described in Example 2 are added to the mixture, while stirring. The melt is then heated wit-hin one hour, while simultaneously distilling olif the alcohol, to 230 C. and the temperature is kept-at 230 to 2400 C. for a further l@ hour. The melt is then poured out, dissolved in water, the dyestutl oxidized out while boiling, separated by suction and washed.

The product dissolves in sulphuric acid to a violet solution, from which on addition of water olive-green flocks separate. From a blue vat cotton isdyed' olivetints which are sensitive to chlorine and acids.

10 parts of the dyestull obtained as described in Example 3 first paragraph, l5

rparts, ofgcalcined sodium carbonateand 15 kmarkable fastness, particularly astness tor chlorine.

A very pure product is obtained by methylatingin nitrobenzene, in which case a part of the dyestulrn cryst'allizes from the hot filtrate.

The methylation may occur in other solvents, for instance in a nitrohydrocarbon, like nitrobenzene. Instead of methylating the hydroxy-compound, it may be ethylated, for instance with toluene sulphonic acid ethylester or diethylsulphate, aralkylated or quite ygenerally treated with any desired etherifying agent. Like yproducts are obtained'by etheriiying the products, which are obtainable by treating thesulphonation lproduct 'of dimethylviolanthrone or iso- .t

violanthrone with caustic alkalies. The product obtained according to Example 4 yield at the etherification products which dye cotton from a blue vat fast blue-green tints.

Example 6 10 parts of the dyestui made as described in the first paragraph of Example 5 are suspended in 30 parts of nitrobenzene and stirred for 3 hours at 80-90" C. with l0 parts of sulphuryl chloride. The dyestuif dissolves in part to a blue grey solution. The mixture is distilled with steam, the residue ltered, washed` and dried.

This product dissolves in concentrated sulphuric acid to a blue solution, from which on addition of water blue fiocl separate. The dyestuii yields a blue vat which dyes cot-V ton grey tints, having a more bluish hue than that of the dyeing of the dyestuff1 before it is halogenated.

vWhat we claim is l. As new products of manufacture the vat dyestuffs of the anthraquinone series obtainable by treating tirstly violanthrone With oleum at temperatures above 100o C., secondly treating the new sulphonic acid thus obtained with alkalies and finally treating the new compound thus obtained with such alkylating agents which introduce alkyl residues containing not more than two carbon atoms, which products ormdarlr powders, dissolving in concentrated sulphuric acid to blue solutions, yielding red-violet vats which dye cotton blue-grey tints of remarkable fa'stness.

2. As a new product of manufacture the vat dyestuff of the anthraquinone series 0btainable by treating firstly violanthrone with oleum at temperatures above 100 C., secondly treating the new sulphonic acid thus obtained with alkalies, and iinally treating the new compound thus obtained with methylat-A ing agents, which productforms a dark powder, dissolving in concentrated `sulph'uric acid to a blue solution, yielding a red-violet vat which dyes cotton a bluegrey tint of revmarkable fastness.

3.V lVlaterialrv dyed with the dyestuil's of claim l. s K l 4c. Material dyed with thel dyestuff of claim 2. i

In witness whereof we have hereunto signed our names this 30th day of September,

. KARL KRAUER. GUsrAv Hass. 

